7582 Chap04

Chapter 4
The First Law of Thermodynamics
In the preceding chapter we categorized all energy interactions between a system and its surroundings either as work or heat. This was a useful starting-point for the introduction of the First Law of Thermodynamics which is essentially the law of conservation of energy formulated in a unified manner to include all energy forms. The first law relates work and heat interactions that occur at the boundary of a system, to the energy possessed or stored by a system which we shall call the internal energy of the system. The emphasis in this chapter will be the application of the first law to a closed system undergoing steady processes. In the next chapter we shall consider open systems and transient or unsteady processes. 4.1 First Law for a Cyclic Process The first law of thermodynamics can be formulated in several different ways. We will adopt the approach, known as the Poincares formulation, because it makes use of the concepts that we are already familiar with from our work in the earlier chapters. The first law states that when a closed system undergoes a cyclic process, the net heat interaction is equal to the net work interaction. This statement of the law can be further elaborated by referring to the cyclic process consisting of n individual processes shown graphically in Fig. 4.1. In our sign convention, we shall take as positive quantities the work done by the system, W and the heat flow into the system, Q. It should be noted that this choice of the signs for work and heat is arbitrary. In Fig. 4.1 we have indicated with arrows the heat flow into the
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Engineering Thermodynamics
Q1 W1 P 1 2 Q2 W2 6 3 Q3 W3 5 4
Fig. 4.1 Cyclic process
system and the work flow out of the system for the different processes that constitute the cycle. The first law for a cyclic process now translates to the following mathematical form
Q1 + Q2 + + Qi + + Qn = W1 + W2 + + Wi + + Wn
Expressed in the compact form Eq. (4.1) reads
i =n i =n
(4.1)
i =1
Qi = Wi
i =1
(4.2)
In the cyclic-integral notation Eq. (4.2) can be written in the form
Q = W
(4.3)
where Q and W are the heat input and work output during an infinitesimal change of state of the system. We recall that both heat and work are path-dependent quantities and are therefore not properties of the system. The symbol , instead of the more common d , is used to differentiate the changes of path-dependent quantities from those of properties. Recall that we demonstrated the path-dependence of work done in chapter 3 and considered particular cases of path independent quantities in worked example 1.4. The first law is applied to cyclic processes in worked examples 4.2, 4.11 and 4.12.
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4.2 First Law for a Change of State Not all processes of importance in engineering thermodynamics are cyclic processes. There are numerous situations where we need to apply the first law to a single process which results in a change of state of the system. We shall now derive the form of the first law for a change of state using the cyclic-form of the law that we have already stated in Sec. 4.1.
P 1
B A
2 V
Fig. 4.2 Change of state
Consider the cyclic process that consists of two processes depicted in Fig. 4.2. The system undergoes a process A resulting in a change of state from 1 to 2, both of which are equilibrium states. The process B returns the system back to state 1 to complete a cycle. Therefore 1A2B1 constitutes a cyclic process to which we apply the first law to obtain the equation
Q12 A + Q21B = W12 A + W21B
(4.4)
We now select an alternative process C to return the state of the system from 2 to 1. Since 1A2C1 is a cyclic process we can apply the first law to obtain the equation
Q12 A + Q21C = W12 A + W21C

Subtracting Eq. (4.5) from Eq. (4.4) and rearranging we have
(4.5)
Q21B W21B = Q21C W21C
(4.6)
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Equation (4.5) shows that the difference between the heat interaction and the work interaction for processes B and C is the same. Since the process C was chosen arbitrarily, we note that the quantity (Q-W) is independent of the process path. Recalling our definition of a property, we can conclude that (Q-W) is a property of the system. This new property is called the internal energy of the system and denoted by the symbol E. In summary, the first law for a single process states that although Q and W are path-dependent quantities, the difference (Q-W) is pathindependent and therefore a property of the system. It depends only on the state of the system. However, as for the physical nature of this new property the first law has little to add. Equation (4.6) can be expressed in terms of the end-states 1 and 2 of a single process in the form
Q1 2 W12 = Increase in internal energy Q1 2 = ( E 2 E1 ) + W12

(4.7) where E 2 and E1 are the internal energy of the system in states 2 and 1 respectively. Q1 2 is the heat input and W1 2 is the work output or done by the system during the process. The differential form of Eq. (4.7) for an infinitesimal change of state is
Q = dE + W
where dE is the increase in the internal energy. The rate-form of Eq. (4.8) is
(4.8)
Q
dt
dE W + dt dt
(4.9)
where dt is the infinitesimal increment of time. In Sec. 3.1 we showed that for a pure mechanical system, like the motion of a body subjected to an external force, the work done is equal to the increase in kinetic energy of the system. We hope to generalize this finding to more complicated systems involving both work and heat interactions. Although the application of Eq. (4.7) appears to be quite
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straightforward, we need to be aware of the following prerequisites before we input the various quantities in the equation. (i) The system, the boundary and the surroundings have to be clearly defined. (ii) The interactions between the system and its surroundings that occur at the boundary have to identified and categorized as work or heat. (iii) All internal energy forms of the system that are likely to be affected by the process and the boundary interactions should be included in the term E. The procedure is best illustrated by considering two practical examples of what are called uncoupled-systems and coupled-systems. The former category of systems is common in basic physics while the latter types are of particular importance in thermodynamics. 4.2.1 An uncoupled-system Figure 4.3 shows a bucket of hot molten metal being hoisted vertically as may happen in a foundry. The bucket and its contents, of fixed mass M, is our system. Its temperature T may be assumed spatially uniform. The centre of mass, G of the bucket is at an elevation z above ground level and the vertical velocity of G is V. The hoisting cable attached to the top outer surface of the system has a tension F. The system interacts with the surrounding ambient which is at a uniform temperature To . Consider the vertical movement dz of the system that happens in a time dt . The work done on system by the external force can be expressed as
W = Fdz
(4.10)
where the negative sign signifies that work is done on the system. From our knowledge of basic mechanics (also see Sec. 3.1)
E KE + E PE = MV 2 / 2 + Mgz
(4.11)
where g is the acceleration due to gravity. EKE and EPE are the kinetic energy and the gravitational potential energy respectively. By virtue of its mass and temperature the system has thermal energy which we shall express as
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F V Q G
z Mg
Fig. 4.3 An uncoupled system
ETH = Mu (T )
(4.12)
At this point we shall not elaborate on the physical nature of thermal energy per unit mass, u (T ) except to state that it depends on the temperature of the system. Since the system is at a higher temperature than the surroundings, there will be a heat flow out of the system, Q . In order to apply the first law to the system we need to list under the category, internal energy, E all the different energy forms that the bucket and its contents may possess. If from our experience, some of these energy forms are not affected by the interactions with the surroundings, then we may choose to ignore these energy forms. For the present system, the energy forms that appear to be pertinent are the kinetic energy, the potential energy and the thermal internal energy. We shall discuss the physical nature of the internal energy in more detail later in this chapter. We now apply the first law in the form of Eq. (4.8) to the infinitesimal change of state of the system
Q = d (E KE + E PE + ETH ) + W
(4.13)
Substituting the expressions from Eqs. (4.10), (4.11) and (4.12) in the above equation we have
Q = d MV 2 / 2 + Mgz + Mu (T ) Fdz
(4.14)
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Although we have combined all the boundary interactions and the internal energy forms in a single equation, Eq. (4.14), our experience tells us that the kinetic and potential energy are affected only by the work done by the tension of the cable and not by the heat loss to the surroundings. Similarly, the thermal internal energy of the system is not affected by the work done by the tension but depends on the heat losses. In view of these observations we can decompose Eq. (4.14) into two uncoupled equations as follows.
d MV 2 / 2 + Mgz = Fdz
and
(4.15) (4.16)
Q = d ( Mu )
The main point that emerges from this example is that for uncoupledsystems each form of boundary interaction only affects one form of internal energy. In the present case the work interaction affects only the kinetic and potential energies as it happens in most mechanical systems. The heat interaction on the other hand, affects only the thermal internal energy, again a familiar situation in heat transfer. The example also helped to cast some light on the physical nature of the new property called internal energy which arose from our formulation of the first law. Two uncoupled systems are considered in worked examples 4.5 and 4.6. 4.2.2 A coupled-system Consider the piston-cylinder apparatus shown in Fig. 4.4, where a light piston of cross sectional area A is attached to a vertical shaft that pushes the piston with a force F. The ambient pressure is Po . The gas in the cylinder is at a temperature T and pressure P and it receives a quantity of heat Q from an external source. The piston is at a level z from the top of the cylinder at time t. As a result of the two boundary interactions the piston moves a distance dz in a time dt. The gas in the cylinder is our system. The work done on the system by the force F and the ambient pressure is given by
W = ( Fdz + Po Adz )
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Po A P
F Z dz
T,V
dQ
Fig. 4.4 A coupled system
Since the piston has negligible mass, the force balance on the piston gives
PA = F + Po A
Hence
W = PAdz
ETE = mu (T , P)
(4.17) (4.18)
The internal energy of the gas is where m is the mass and u is the thermal internal energy per unit mass. Applying the first law in the form of Eq. (4.8) we have
Q = dETH + W
Substituting in Eq. (4.19) from Eqs. (4.17) and (4.18)
(4.19) (4.20)
mdu (T , P ) = Q P(T , V ) Adz
We observe from Eq. (4.20) that the internal energy of the system is affected by both the heat interaction and the work interaction. Therefore the system is called a coupled-system. Such systems have wide engineering applications, especially in thermal power systems. 4.3 Internal Energy A Thermodynamic Property Our formulation of the first law predicted the existence of a property called the internal energy. In order to understand the physical nature of
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this new property we need to recall some of the common energy transformations from our earlier studies of basic physics. Two forms of energy that arise in the study of mechanics are the kinetic energy and the gravitational potential energy. Both these forms of energy are possessed by bodies or systems in motion and are therefore forms of internal energy (see Sec. 3.1). Kinetic and potential energy are associated with the system as a whole and are often called energy forms of the bulk motion. Another common form of energy is the internal thermal energy associated with the temperature of a system. Application of the simple kinetic theory to a monatomic ideal gas in Sec. 2.8 revealed that the absolute temperature of the gas is a measure of the mean translational kinetic energy of the molecules. For more complicated polyatomic gases, the temperature is related to the number of different modes of molecular motion that include translation, rotation, vibration and others. The thermal internal energy, usually denoted by U, plays a very important role in thermodynamics and will be explored in greater detail in the subsequent sections of this chapter. Several other forms of internal energy, although not frequently encountered in this book, need to be mentioned here. A compressed or extended spring possesses strain energy which is a form of internal potential energy. A fluid film like a soap bubble has surface energy which is also a form of internal energy. A system subjected to an electric or a magnetic field could possess stored energy by virtue of its interaction with these fields as it does when it is displaced in a gravitational field. There are also forms of internal energy that could undergo transformation to other forms of internal energy as it happens in combustion processes and nuclear fission reactions. In the case of combustion, the chemical binding energy of the fuel, a form of internal energy, is first transformed into thermal internal energy of the products of the chemical reaction which manifests as an increase of temperature. The thermal internal energy in turn produces a heat interaction or a work interaction at the boundary of the combustion system depending on the application. In the case of a fuel element in a nuclear reactor, the fission reaction converts the nuclear binding energy of the fuel first into thermal internal
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energy which then results in a heat interaction at the boundary between the fuel element and the coolant. In summary, the internal energy of a system could, in general, include a number of different energy forms. These include, kinetic energy, potential energy, thermal internal energy, chemical binding energy, surface energy, nuclear binding energy and others. However, in most of the systems and applications of interest in this book we would be dealing mainly with only three forms of internal energy. These are the kinetic energy, the gravitational potential energy and the thermal internal energy. Expressed mathematically
E = MV 2 / 2 + Mgz + U
(4.21)
where M is the mass of the system, V is the velocity, g is the acceleration due to gravity and z is the vertical height above a datum level where the potential energy is taken as zero. U is the thermal internal energy associated with microscopic-level motion of the molecules that constitute the system. 4.4 State Postulate The state postulate is a statement on the number of independent properties required to specify the state of a system. For a system involving only compressible work, ( PdV ) two intensive properties are sufficient to completely specify an equilibrium state of the system. The above statement is sometimes called the two-property rule. 4.5 Internal Energy and Heat Capacities Having discussed the nature of internal energy, E in general terms, we will now consider a few special situations where the nature of a substance allows us to develop methods to calculate and also to measure the internal energy. These include simple compressible substances and pure substances. It is to be noted that by internal energy we now mean the part of E that depends on the temperature and we shall denote it by the symbol U.
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4.5.1 Heat capacity at constant volume From the state postulate it follows that for a simple compressible system the thermal internal energy U may be expressed in terms of the temperature T and the volume V
U = U (T , V )
The heat capacity at constant volume, CV is defined as
(4.22)
U CV = T V
(4.23)
The heat capacity, CV is a property of the system because it is the slope of the graph of U versus T at constant V. We recall that U, T and V are properties of the system. We now consider a constant volume process that would enable the measurement of CV . The substance is contained within a rigid boundary and is heated in a quasi-static manner by supplying a small quantity of heat Q which results in an increase of temperature of dT . Since boundary is rigid the work done W is zero. The system as a whole is stationary, and therefore the change in bulk kinetic energy and potential energy are also zero. Applying the first law in the form of Eq. (4.8) we have
Q = dU
It follows from Eqs. (4.24) and (4.23) that
(4.24)
Q dU U = = = CV dT const .V dT const .V T V
(4.25)
Equation (4.25) shows that a constant volume heating process offers a possible method to determine CV by measuring the heat input and the rise in temperature in the process. It should be noted that Eq. (4.25) which relates CV to the heat input, Q is only true for a constant volume process. However, from the general definition, given by Eq. (4.23), we see that CV is a system property which is independent of the processes involved. It is clear that CV is not defined for phase change processes like evaporation and condensation where the temperature of the system is constant.
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4.5.2 Enthalpy We now introduce a new property called enthalpy that is closely related to the thermal internal energy U. Enthalpy is most useful in the analysis of processes in open-systems which will be the subject of the next chapter. As a prelude, we use a constant pressure process to demonstrate the usefulness of enthalpy as a property. Consider the piston-cylinder arrangement where the pressure, P of the gas within the cylinder is maintained constant by keeping the weights on the piston fixed. A small quantity of heat, Q is supplied to the gas in a quasi-static manner resulting in an increase in volume dV . The work done by the gas is PdV . Applying the first law to this process we have
Q = dU + PdV
(4.26)
Since the pressure is constant during the process we could rewrite Eq. (4.26) as
Q = d (U + PV )
(4.27)
Now the quantity (U + PV ) is a property because U, P and V are all properties of the system. This new property is called enthalpy which is denoted by the symbol H. Hence we could write Eq. (4.27) in the form
Q = d (U + PV ) = dH
(4.28)
It should be emphasized that the change in enthalpy is equal to the magnitude of the heat interaction only for a constant pressure process. However, being a property, the enthalpy is a function of the state of the system and therefore independent of the processes undergone by the system. 4.5.3 Heat capacity at constant pressure The system property called the heat capacity at constant pressure, C P is related directly to the enthalpy of the system. Following the two-property rule we can express the enthalpy as a function of T and P.
H = H (T , P )
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We define C P as
H CP = T P
(4.29)
The heat capacity, C P is a property because it is the slope of the graph of H versus T at constant P. Note that the three quantities H, T and P are properties of the system. A constant pressure process offers a method to determine C P by measuring the heat input and the corresponding rise in temperature. Consider the piston-cylinder arrangement where heat is supplied to the system at constant pressure. Applying Eq. (4.28) to the constant pressure process we have
Q = dH
It follows from Eqs. (4.30) and (4.29) that
(4.30)
Q dH H = = = CP dT const . P dT const .P T P
(4.31)
It should be noted that Eq. (4.31) which relates C P to the heat input, Q is only true for a constant pressure process. However, from the general definition given Eq. (4.29) we see that C P is a system property which is independent of the processes involved. It is clear that C P is not defined for phase change processes where the temperature of the system is constant. 4.6 Properties of Ideal Gases The ideal gas is a useful model for engineering analysis of thermodynamic systems. In chapter 2 we introduced the equation of state of the ideal gas which is a relationship between the properties P, V and T. In this section we shall extend the ideal gas model to include its energy-related properties.
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4.6.1 Internal energy, enthalpy and heat capacities of an ideal gas The two-property rule for a simple compressible pure substance states that, in general, the thermal internal energy, U is a function of two other properties. However, using the first and second laws of thermodynamics and the equation of state it can be proved that the internal energy of an ideal gas is a function of temperature only. Therefore
U = U (T )
Now the enthalpy of an ideal gas is given by
(4.32) (4.33)
H = U (T ) + PV
Substituting in Eq. (4.33) from the ideal gas equation of state, PV = mRT , we have
H = U (T ) + mRT = H (T )
(4.34)
Equation (4.34) shows that the enthalpy of an ideal gas is also a function of temperature only. Hence the heat capacities of an ideal gas can be expressed in the form
U dU CV = = T V dT H dH CP = = T P dT
(4.35)
(4.36)
We are now able to write two simple relations between the internal energy, the enthalpy and the heat capacities of an ideal gas. These follow directly from Eqs. (4.35) and (4.36) as
dU = CV dT
and
(4.37) (4.38) (4.39) (4.40)
dH = C P dT
dH = dU + mRdT CP dT = CV dT + mRdT
Differentiation of Eq. (4.34) gives Substituting from Eqs. (4.37) and (4.38) in the above equation we have
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Hence
C P CV = mR
(4.41)
We define the heat capacities per unit mass or the specific heat capacities as
c v = CV / m
and
c p = CP / m
Equation (4.41) can be expressed in terms of the specific heat capacities as
c p cv = R
The molar-from of Eq. (4.42) is
(4.42)
c p cv = R
(4.43)
where cv and c p are the specific heat capacities per mole of the ideal gas and R is the universal gas constant. Summarized below are the typical units of the various energy-related properties introduced in this chapter.
[U ] = J, [H ] = J, [CV ] = JK-1, [C P ] = JK-1,

[cv ] = Jkg-1K-1, [c p ] = Jkg-1K-1, [R] = Jkg-1K-1 [cv ] = Jkmol-1K-1, [c p ] = Jkmol-1K-1, [ R ] = Jkmol-1K-1
4.6.2 Heat capacities and kinetic theory In Sec. 2.7 we applied the kinetic theory to an ideal monatomic gas to obtain an expression for the temperature in terms of the molecular kinetic energy. We shall now extend this approach to relate the internal energy and the heat capacities of an ideal gas to the energy of the constituent molecules. Consider the monatomic gas, the molecules of which are free to move in three mutually perpendicular directions. The translation in each direction constitutes a degree of freedom and therefore the monatomic gas has 3 degrees of freedom. The internal energy per mole of gas can be written as
u = N A m C 2 / 2
(4.44)
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where m is the mass of a molecule, C is the average molecular speed and N A is the number of molecules per mole, which is called the Avogadros number. But mN A = M , the molar mass of the gas. Therefore from Eq. (4.44), we have
u = M C 2 /2
(4.45)
In Sec. 2.7 we obtained the following equation for the temperature.
T = MC 2 / 3R
From Eqs. (4.45) and (4.46) it follows that
(4.46)
u = 3R T / 2
Now the enthalpy per mole of the gas is given by
(4.47)
h = u + R T = 5R T / 2
The molar specific heat capacities of the ideal gas are obtained as
(4.48)
cv = du / dT = 3R / 2
(4.49) (4.50)
c p = dh / dT = 5R / 2
In order to extend the above analysis to diatomic gases, we invoke the principle of equipartition of energy which states that the total energy of a molecule is shared equally between the different degrees of freedom of the molecule. Hence for a monatomic gas which has three translational degrees of freedom, it follows from Eq. (4.47) that the internal energy per degree of freedom is R T / 2 . Moreover, from Eq. (4.49) the molar specific capacity at constant volume per degree of freedom becomes R /2. Now consider a diatomic molecule which can be modeled as two point masses connected by a spring. The centre of mass of the molecule has three translational degrees of freedom. In addition, the molecule can rotate about two mutually perpendicular directions. Being point masses, the rotation about the axis connecting the molecule will acquire no rotational kinetic energy. Furthermore, the two masses could vibrate
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along the connecting axis as a spring-mass system with strain energy stored in the spring and vibrational kinetic energy stored in the two masses. The latter motion constitutes two degrees of freedom. Therefore the diatomic molecule has 7 degrees of freedom. From the principle of equipartition of energy it follows that the diatomic molecule could have a molar specific capacity of up to 7 R / 2 . The number of degrees of freedom that are excited and therefore participate in the internal energy storage depends on the temperature of the gas. At low temperatures only the three translational modes are excited, and cv = 3R / 2 . At intermediate temperatures the two rotational modes are also excited and cv = 5 R / 2 . When temperature is very high all 7 modes participate in the energy sharing.
Table 4.1 Molar Specific heat capacities of three gases* Ts(K) 300 600 Gas cv cp = cv +R cv cp = cv +R CO 20.8 29.1 22.1 30.4 N2 20.8 29.1 21.8 30.1 H2 20.3 28.6 20.7 29.1
*The values of cv [kJkmol-1K-1] and cp = cv + R, predicted by the kinetic theory are: 3R/ 2 = 12.47, 5R/ 2 = 20.78, 7R/ 2 = 29.1
The variation of cv with temperature predicted by the kinetic theory is depicted in Fig. 4.5. The gradual change seen between the values for the different degrees of freedom is because all the molecules of the gas do not undergo the transition from one level to the next at the same temperature. Table 4.1 gives the molar specific heat capacities of three gases obtained using the tabulated data from [4]. Notice that the values predicted by the kinetic theory, listed below Table 4.1, are in good agreement with the corresponding values in the table.
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4R
Cv
3R Vibration
2R
Rotation
R Translation
Cv - monatomic gas
Temperature , T
Fig. 4.5 Variation of
cv
predicted by the Kinetic Theory
4.7 Temperature Dependence of Heat Capacity Accounting for the temperature dependence of the specific heat capacities of ideal gases in engineering computations could be quite tedious. When the temperature change involved in a process is not too large, the specific heat capacities of the ideal gas may be assumed constant. From Fig. 4.5 we notice this to be true as long as the number of degrees of freedom of the molecules remain the same. This approximation is very common in engineering analysis and we shall use it in the worked examples in this chapter. However, when the temperature range of interest is relatively wide, as in combustion processes, ignoring the temperature dependence of the specific heat capacities may lead to significant errors in the computed quantities. In such situations, the temperature dependence could be included in the analysis by fitting polynomials to the tabulated heat capacity data in the form
C v = f (T ) = a o + a1T + a 2T 2 + a3T 3 +
(4.51)
where a1 , a 2 and a3 are constants. The temperature dependence of the specific heat capacity is considered in worked example 4.19.
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4.8 Internal Energy and Enthalpy of a Pure Substance In Sec. 2.5 we discussed the use of tabulated property data for a pure substance that undergoes phase change focusing mainly on P, v and T. We shall now extend the discussion to the tabulation of internal energy and enthalpy. Typical values of specific internal energy and specific enthalpy of water for saturated and superheated conditions, extracted from [4], are shown in Tables 4.2 and 4.3 respectively. For sub-cooled or compressed liquids we ignore the effects of the pressure and use the saturated liquid internal energy u f , and enthalpy h f at the desired temperature. For saturated liquids and dry saturated vapors the values of ug and hg are directly available in Table 4.2. where linear interpolation may be needed to determine intermediate values. For wet vapors we use the expressions given by Eqs. (4.52) and (4.53), similar to that used for the specific volume, to compute the mean internal energy and enthalpy of the mixture.
Table 4.2 Internal energy and enthalpy of saturated water and steam P( bar) 0.05 10 Ts(oC) 32.9 179.9 uf (kJkg-1) 138 762 ug (kJkg-1) 2420 2584 hf (kJkg-1) 138 763 hg (kJkg-1) 2561 2778
u = xu g + (1 x)u f h = xhg + (1 x)h f
(4.52) (4.53)
where x is the vapor quality. For superheated vapors the internal energy and enthalpy are obtained by interpolation if data at the required temperature and pressure are not directly tabulated. (see Table 4.3).
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Engineering Thermodynamics Table 4.3 Internal energy and enthalpy of superheated water vapor P( bar) [Ts(oC)] 5 [151.8] 50 [263.9] T (oC) u (kJkg-1) h (kJkg-1) u (kJkg-1) h (kJkg-1) 300 2804 3065 2700 2927 350 2883 3168 2810 3070 400 2963 3272 2907 3196
In summary, a procedure similar to that used in chapter 2 to extract the specific volume from tabulated data can be adopted to obtain the internal and the enthalpy for pure substances. It is important to note that the ideal gas equation of state is not applicable to wet steam and superheated steam. For solids, the internal energy U and the enthalpy H are equal because of their very low compressibility. Therefore the following relation may be used to describe their behavior
dU = dH = mcdT
(4.54)
where c is the specific heat capacity. Far below their critical temperature many liquids have a very low compressibility, similar to solids. In these situations they may be treated incompressible and as a first-order approximation, Eq. (4.54) may be used to determine the change in internal energy. The temperature dependence of the specific heat capacity may be included in engineering computations by fitting a polynomial, similar to Eq. (4.51), to the tabulated specific heat capacity data. 4.9 Worked Examples Example 4.1 The heat input Q, the work output W, the initial and final internal energies U 1 and U 2 respectively and the increase in internal energy U for 5 processes of a closed system are tabulated below. Obtain the missing quantities.
The First Law of Thermodynamics Process a b c d e Qin(kJ) 12 25 -10 10 ? Wout(kJ) 6 -8 ? -6 25 U1(kJ) 81 ? ? ? 58 U2(kJ) ? -13 60 -10 ? U(kJ) ? ? -18 ? 16
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Solution We shall use the first law for a change of state to determine the missing quantities in the table above. The two relevant equations are:
Qin = U 2 U 1 + Wout
and (a)
(E4.1.1)
U = U 2 U 1 12 = U 2 81 + 6 , 25 = 13 U 1 8 ,
10 = 18 + Wout ,
(E4.1.2)
U 2 = 87 , U 1 = 46 ,
Wout = 8 ,
U = 6 U = 33
(b)
(c)
U 1 = 78
U = 16
(d)
10 = 10 U 1 6 ,
Qin = 16 + 25 ,
U 1 = 26 ,
Qin = 41 ,
(e)
U 2 = 74
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Example 4.2 Figure E4.2 shows the P-V diagram for the change of state of a closed system from a to b. The internal energies at states a and 2 are 2 kJ and 42 kJ respectively. During the process a-1-b the heat input and the work output of the system are 82 kJ and 32 kJ respectively. When the same change of state is achieved through the process a-2-b, the work output of the system is 12 kJ. When the state of the system is changed from b to a through the process b-3-a, the work output is 22 kJ. Calculate (i) the heat input during the process a-2-b, (ii) the heat interaction during the process b-3-a and (iii) the heat interactions during the processes a-2 and 2-b. Solution The given data are:
Ua = 2 , Qa1b = 82 ,
U 2 = 42 ,
Wa 2b = 12 ,
Wa1b = 32 , Wb 3a = 22
Applying the first law to a change of state
Qin = U 2 U 1 + Wout
The above equation is now applied to the various processes shown in Fig. E4.2
Qa1b = U b U a + Wa1b = 82 = U b U a + 32 U b U a = 50 kJ Qa 2b = U b U a + Wa 2b = 50 +12 = 62 kJ Qb 3a = U a U b + Wb3a = 50 + 22 = 28 kJ Wa 2b = Wa 2 + W * 2b = 12 = Wa 2 + 0 , Wa 2 = 12 kJ

P
153
3 a 2
V
Fig. E4.2 P-V diagram
Wa1b = W * a1 + W1b = 32 = W1b + 0 ,
W1b = 32 kJ
Qa 2 = U 2 U a + Wa 2 = (42 2) + 12 = 52 kJ Qa 2b = Qa 2 + Q2b = 52 + Q2b = 62 , Q2b = 10 kJ
* Note that the work interaction in a quasi-static constant-volume process is zero. Example 4.3 In a heat treatment operation, a steel component of mass 0.75 kg at an initial temperature of 200oC is cooled to 50oC by placing it in a steel tank containing water at an initial temperature of 25oC. The steel tank has a mass of 1.2 kg and is well-insulated. The specific heat capacities of water and steel are 4.2 kJkg-1K-1 and 0.48 kJkg-1K-1 respectively. (a) Calculate the mass of water. (b) Considering (i) the steel component, (ii) the tank and (iii) the water as closed systems calculate the heat interaction, the work interaction and the change of internal energy. Solution Consider the steel component and the tank of water as a closed system. The sub-scripts s, w and t represent quantities related to the steel component, the water and the tank respectively. (see Fig. E4.3). Choose 0oC as the reference state where the internal energy, U is zero. Then the initial internal energy of the system is
U 1 = ( m s c s ) 200 + (mw c w ) 25 + (mt ct ) 25
154
tank -t water - w
Fig. E4.3 Heat treatment operation
The final internal energy is
U 2 = (m s c s ) 50 + (mw c w ) 50 + (mt ct ) 50
where m is the mass and c is the specific heat capacity at constant volume. Note that for a solid and a liquid the heat capacities at constant volume and constant pressure can be assumed equal because of their relatively low compressibility. Applying the first law to the closed system we have
Q12 = U 2 U1 + W12
(E4.3.1)
Since the tank is well-insulated Q 12 = 0 . Assuming the tank to be rigid, W 12= 0 . Substitute these conditions in Eq. (E4.3.1). Hence
U 2 = U1
Substituting the given numerical data in the above equation
0.75 0.48 (200 50) + 1.2 0.48 (25 50)

= mw 4.2 (50 25)
The mass of water, m w = 0.377 kg. We recall that in applying the first law to a closed system in the form of Eq. (E4.3.1), we follow the sign convention where the heat inflow, the work output and the increase in internal energy are positive quantities. Apply Eq. (E4.3.1) to the steel component which has a boundary with the water. Assume that the change in volume of the steel is negligible.
Ws w = 0
155
U s = ms c s (50 200) = 0.75 0.48 150 = 54 kJ Qw s = U s + Ws w = 54 kJ

Apply Eq. (E4.3.1) to the steel tank which has a boundary with the water. Neglecting any change in volume.
Wt w = 0 U t = mt ct (50 25) = 1.2 0.48 25 = 14.4 kJ Qwt = Ut + Wt w = 14.4 kJ

Apply Eq. (E4.3.1) to the water which has one boundary with the steel component and a second boundary with the tank. Neglect any change in volume.
W w t = 0
and
Ww s = 0
U w = m w c w (50 25) = 0.377 4.2 25 = 39.59 kJ Qs w + Qt w = U w + Wwt + Ww s = 39.6 kJ

Example 4.4 A well-insulated steel vessel of mass 1.2 kg contains 4 kg of water. A paddle wheel immersed in the water is driven by a motor that receives power from a storage battery as shown in Fig. E4.4. The heat capacity of the paddle wheel is 0.8 kJK-1 and the thin non-conducting shaft connecting it to the motor has negligible heat capacity. The temperatures of the water, the wheel and the vessel which may be assumed uniform, is found to be increasing at the rate of 0.012oCs-1 at a certain instant. The specific heat capacities of water and steel are 4.2 kJkg-1K-1 and 0.48 kJkg-1K-1 respectively. Considering (i) the vessel, (ii) the paddle wheel and water, (iii) the motor, (iv) the battery and (v) the composite system as closed-systems, calculate the heat interaction, the work interaction and the rate of change of internal energy in Watts.
156
Solution The sub-scripts v, w, m, b, s and a denote quantities related to the vessel, the wheel and water, the motor, the battery, the composite system and the surroundings respectively. To each system we apply the rate-form of the first law
=U +W Q
(E4.4.1)
where the dot over a quantity represents differentiation, d/dt, t being time. Consider the vessel as a closed system with an interacting boundary with the water and the wheel. The vessel is insulated on the outside. Applying the first law to the vessel we have
Q wv = U v + Wv w
V W Q M a
Fig. E4.4 Insulated tank with paddle wheel
(E4.4.2)
The work interaction, W v w = 0 . The rate of change of internal energy is = m c (dT / dt ) = 1.2 0.48 0.012 = 6.912 W U v v v w
Substituting in Eq. (E4.4.2)
Q w v = 6.912 W
The water and the paddle wheel form a closed system, the boundary being the inside of the vessel and the shaft penetrating it. Applying the first law to the water and paddle wheel we have
Q v w = U w + W w v + W w m
(E4.4.3)
157
Now and
W w v = 0 = m c (dT / dt ) + m c (dT / dt ) U w w w w wh wh wh = 4 4.2 0.012 + 0.8 0.012 = 211.2 W U w
Substituting in Eq. (E4.4.3)
6.912 = 211.2 + 0 + W w m W w m = 218.11 W

Applying the first law to the motor as a closed system we have
Q a m = U m + Wm w + W m b
Assume that the motor experiences no heat losses or internal energy changes. Therefore from the above equation
W m w + Wm b = 0 = 218.11 + Wm b
The work input from the battery to the motor is
W b m = 218.11 W
Now consider the battery as a closed system. Applying the first law
Q a b = U b + Wb m
Assume that there is no heat loss from the battery to the surroundings. Therefore from the above equation
+W U b bm = 0 = W U b b m = 281.11 W
Apply the first law to the composite system consisting of the vessel, the motor and the battery. The work interaction and the heat interaction with the surroundings are both zero. Therefore
Q a s = U s + Ws a = U w + U v + U b + Ws a = 6.912 + 211.2 218.11 = 0 U s
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Example 4.5 A steel projectile of mass 0.003 kg moving at 250 ms-1 is fired into a stationary block of mass 5 kg of negligible thermal capacity. Initially the projectile and the block are at 20oC. Calculate (i) the speed of the block and the projectile soon after they start to move as a composite body and (ii) the temperature of the projectile at that stage. The heat capacity of steel is 0.48 kJkg-1K-1. Solution We apply the law of conservation of momentum to determine the speed after impact when the projectile and the block move as a composite body. Thus
m pV p = (m p + mb )Vsf
(E4.5.1)
where V is the velocity, m is the mass and sub-scripts p and b denote quantities related to the projectile and the block respectively. Let Vsf be the velocity of the composite body after the impact.
system mp
F
Vsf mb
Vp
Fig. E4.5 Projectile in block
Substituting numerical values in Eq. (E4.5.1)
Vsf = 3 10 3 250 /(5 + 3 10 3 ) = 0.15 ms-1

As the projectile plows into the block it does work to overcome the frictional force. This frictional work, which occurs at the interface between the projectile and the block results in a heat interaction. As a consequence the internal thermal energy of the projectile and the block increase. However, the heat interaction between the system and
159
surroundings is negligibly small. Also there is no work transfer to the surroundings, because the frictional work is internal to the system consisting of the projectile and the block. The block has negligible thermal capacity and therefore it does not store any thermal internal energy. We write the following expressions for the total internal energy of the projectile and the block before and after the impact. The thermal internal energy is taken to be zero at the reference state of 0oC.
Ei = m pV pi / 2 + m p c p T pi + mb cbTbi E f = (m p + mb )Vsf / 2 + m p c p T pf + mb cbTbf

Substituting numerical values in the two equations above we have
2
E i = 0.003 (250) 2 / 2 + 0.003 0.48 10 3 20
(E4.5.2) (E4.5.3)
E f = 5.003 (0.15) 2 / 2 + 0.003 0.48 10 3 T pf
Consider the projectile and the block as a closed system for which the work and heat interactions are both zero. Applying the first law
Q = E f Ei + W E f Ei = 0
(E4.5.4) (E4.5.5)
Substituting from Eqs. (E4.5.2) and (E4.5.3) in Eq. (E5.4.5) we obtain the temperature of the projectile as it starts to move with the block as a composite body as T pf = 85.1 oC Example 4.6 Figure E4.6 shows a braking-device used to stop a freelyrotating flywheel of a machine. The brake is applied by pressing the stationary disc A against the disc B attached to the flywheel. The heat exchange between A and B and the surroundings is negligible. At some instant when the brake is in operation the speed of the flywheel is 10 rs-1, and the speed is decreasing at the rate of 0.5 rs-2. The temperature of disc B is observed to be increasing at the rate of 0.02oCs-1. The effective moment of inertia of the flywheel is 5.0 kgm2. The thermal capacities of the discs A and B are 0.3 kJK-1 and 0.75 kJK-1
160
respectively. Calculate (i) the rate of increase of the temperature of disc A, and (ii) the heat interactions for discs A and B. Solution Let the sub-scripts w, a, b, s and o represent quantities related to the wheel, the disc A, the disc B, the composite system and the surroundings respectively. Applying the rate-form of the first law to the whole system we have
Q s o = E s + W s o
B A Fb Flywheel
(E4.6.1)
Fig. E4.6 Flywheel with disc brake
consists of the rotational kinetic energy The total internal energy, E s of the flywheel and the thermal internal energies of the two discs A and B. The heat transfer and the work transfer from the composite system to the surroundings are both zero. Therefore
= d I 2 / 2 + U +U =0 E s a b dt
(E4.6.2)
= [I (d / dt ) + (mc) (dT / dt ) + (mc) (dT / dt )] = 0 E s a a b b

Substituting the given numerical values we have
= 5 10 0.5 10 3 + 0.3 (dT / dt ) + 0.75 0.02 = 0 E s a

Hence
dTa / dt = 0.033 oCs-1.
Now consider the disc A as a closed system. The boundary is drawn just inside A so that the rubbing interface between A and B is outside the boundary. Therefore the work interaction due to the frictional torque at
161
the interface is outside this boundary. Applying the first law to this system we have
+Q Q ia o a = U a + Wa o + Wa i
(E4.6.3)
where the sub-script i denotes the interface. The heat interaction with the surroundings, Q o a = 0 , the work interaction, Wa o with the surroundings and the work interaction, Wi a with the interface are zero. Hence Eq. (E4.6.3) becomes
Q i a = U a = ( mc ) a (dTa / dt ) = 0.3 0.0330 = 0.0099 kW

Therefore the heat flow rate into disc A is 0.0099 kW. Applying Newtons second law to the system
I (d / dt ) = f
(E4.6.4)
where f is the frictional torque at the rubbing interface between A and B. Multiplying Eq. (E4.6.4) by we have
d = f dt
(E4.6.5)
Equation (E4.6.5) can be written as
d I 2 / 2 = f (d / dt ) = W f dt
(E4.6.6)
where is the angle of rotation, so that the angular speed, = d / dt . . Equation (E4.6.6) shows that The rate of frictional work done is W f the rate of decrease of the rotational kinetic energy of the wheel is equal to the rate of work done by the frictional torque at any instant. Substituting numerical values in Eq. (E4.6.6)
= I (d / dt ) = 5 10 0.5 10 3 = 0.025 kW W f
Now apply the first law to the interface between discs A and B where the frictional work is being done.
Q a i + Qb i = U i + W f
The internal energy storage in the interface, U i is negligible.
162
Substituting numerical values in the above equation we have
0.0099 + Qbi = 0 0.025 = 0.0151 kW Therefore the heat flow into disc B is, Q
i b
In summary, the rate of decrease in the rotational kinetic energy of the wheel is equal to the rate of frictional work done at the interface between A and B. The frictional work in turn is converted to two heat interactions with A and B at their interface. The thermal internal energy of A and B increase as a result of these heat flows. Example 4.7 A well-insulated rigid vessel, divided by a partition, has 0.2 kmol of carbon dioxide at 30oC and 2 bar in one section and 3 kmol of hydrogen gas at 40oC and 4 bar in the other section. The partition is removed and the gases mix. Determine (i) the final equilibrium temperature and pressure of the gas mixture, and (ii) the volume of the vessel. The specific heat capacity, c p of hydrogen and carbon dioxide are 14.35 Jkg-1K-1 and 0.84 Jkg-1K-1 respectively. Solution Consider the vessel as a closed system. Applying the first law to the system we have
Qin = U f U i + Wout
Since the volume of the vessel is fixed, the boundary work done is zero. Being well-insulated, the heat interaction with the surroundings is also zero. Therefore the final internal energy, U f is equal to the initial internal energy U i .
m h cvhT fh + mc cvcT fc = m h cvhTih + mc cvc Tic
(E4.7.1)
where the sub-scripts h and c refer to hydrogen and carbon dioxide respectively. Using the relation c p cv = R / M , M being the molar mass, we obtain the specific heat capacities for hydrogen and carbon dioxide as
cvh = 14.35 8.3145 / 2 = 10.192 Jkg-1K-1 cvc = 0.84 8.3145 / 44 = 0.651 Jkg-1K-1
163
The mass of hydrogen and carbon dioxide are
mh = nh M h = 3 2 = 6 kg mc = nc M c = 0.2 44 = 8.8 kg
In the final equilibrium state, the temperature, T f of the gas mixture is uniform. Hence
T fh = T fc = T f
Substituting numerical values in Eq. (E4.7.1) we have
Tf =
8.8 0.651 300 + 6 10.192 313 = 311.88 K 8.8 0.651 + 10.192 6
Applying the molar-form of the ideal gas equation to the initial state we obtain
V = V1 + V2 = n h R Tih / Pih + nc R Tic / Pic

V = 3 8.3145 313 / 400 + 0.2 8.3145 303 / 200 = 22.04 m3
Applying the ideal gas equation to the final state
Pf =
( n h + nc ) R T f V
3.2 8.3145 311.88 = 376.5 kPa 22.04
Example 4.8 A rigid vessel A, containing 0.35 m3 of nitrogen at 65oC and 6 bar, is connected to a rigid vessel B, that is initially evacuated (see Fig. E4.8). The valve in the connecting pipe is initially closed. The valve is now opened, and nitrogen flows into B until the pressure and temperature in B become 1.5 bar and 25oC respectively. The valve is then closed and the final equilibrium pressure and temperature in A are 4 bar and 50oC respectively. The specific heat capacity, c p of nitrogen is 1.041 kJkg-1K-1. Calculate (i) the volume of B and (ii) the total heat interaction between the nitrogen and the surroundings. Assume that the volumes of the pipe and valve are negligibly small. Solution The gas constant for nitrogen is
R = R / M = 8.3145 / 28 = 0.297 kJkg-1K-1
164
The initial and final mass of nitrogen in vessel A and the final mass of nitrogen in vessel B are obtained by applying the ideal gas equation in the form, m = PV / RT . The volumes of the pipe and valve are negligible.
A V
Fig. E4.8 Gas flow between two vessels
Initial mass in A is
m Ai =
0.35 6 10 5 = 2.09 kg 0.297 10 3 338 0.35 4 10 5 = 1.459 kg 0.297 10 3 323
Similarly, the final mass in A is
m Af =
The mass of nitrogen transferred to B is
mBf = mAi mAf = 2.09 1.459 = 0.631 kg

The volume of B is obtained by applying the ideal gas equation to the nitrogen in B
VB =
0.631 0.297 10 3 298 = 0.372 m3 1.5 10 5
Consider a closed system consisting of the vessels A and B, the pipe and the valve. The work done by this system is zero because the boundary is fixed. Applying the first law we obtain
165
Qin = U f U i = (m Af cv T Af + m Bf cv TBf ) m Ai cv T Ai
Now Hence
cv = cp R = 1.041 0.297 = 0.744 kJkg-1K-1
Qin = (1.459 0.744 323 + 0.631 0.744 298)

2.09 0.744 338 = 35.06 kW
The rate of heat flow out of the system is 35.06 kW. Example 4.9 A well-insulated rigid vessel has two compartments that are separated by a membrane. One section of the vessel contains 0.9 kg of water at 7 bar and 72oC. The other section is evacuated. The membrane ruptures and the water fills the entire volume of the vessel. The final equilibrium pressure is 0.14 bar. Calculate (i) the quality and temperature of the steam in the final state and (ii) the volume of the vessel. Solution (i) Consider the water in the compartment as a closed system. Applying the first law for the change of state from the initial (i) to the final ( f ) we have
Qin = U f U i + Wout
(E4.9.1)
When the membrane separating the two compartments ruptures the water undergoes a free expansion without any resistance. In other words, the volume of water increases to fill the entire vessel but it encounters no resistance in doing so. Therefore the work done in such a process, usually called a fully-unresisted expansion, is zero. Since the vessel is well-insulated the heat exchange with the surroundings is also zero. Hence from Eq. (E4.9.1) we have
U f = Ui
(E4.9.2)
In the initial state the water at 72oC is a sub-cooled liquid because its temperature is below the saturation temperature at 7 bar, which is 165oC. For the sub-cooled liquid we ignore the effect of pressure and obtain the internal energy from the steam tables in [4] by selecting the saturated liquid internal energy at 72oC. Therefore u i = 302 kJkg-1. In the final
166
state at 0.14 bar we assume that the vessel contains wet steam with a quality x f . Hence
u fs = x f u g + (1 x f )u f
where
(E4.9.3)
u f = 220 kJkg-1
and
u g = 2446 kJkg-1
are respectively the saturated liquid and vapor internal energies at 0.14 bar. Substituting in Eq. (E4.9.2) from Eq. (E4.9.3) we have
m s [ x f u g + (1 x f )u f ] = U i = m s 302
where m s is the mass of water. Substituting numerical values
[ x f 2446 + (1 x f ) 220] = 302

Hence
(E4.9.4)
x f = 0.0368
The final temperature is the saturated temperature at 0.14 bar which from the steam tables [4] is 52.6oC. Note that if the quality, x f given by Eq. (E4.9.4), was greater than one, then we conclude that the steam is superheated after the expansion and obtain the final temperature from the superheated steam tables. (ii) The final specific volume is given by
v fs = x f v g + (1 x f )v f
(E4.9.5)
The saturated liquid and vapor specific volumes at 0.14 bar are obtained from the steam tables in [4] as
v f = 0.1013 10 2 m3kg-1 and
v g = 10.69 m3kg-1
respectively. Substituting these values in Eq. (E4.9.5) we have
v fs = 0.0368 10.69 + (1 0.0368) 0.1013 10 2 m3kg-1

v fs = 0.3948 m3kg-1
In the final state the steam occupies the entire vessel. Therefore volume of the vessel is given by
Vv = m s v fs = 0.9 0.3948 = 0.3553 m3
167
Example 4.10 An ideal gas undergoes a quasi-static, adiabatic expansion from an initial state ( P1 , V1 , T1 ) to a final state ( P2 , V2 , T2 ). (a) Obtain in differential-form the P-V relation for the process in terms of the specific heat capacities c p and c v of the ideal gas. (b) If the specific heat capacities are constant, obtain the P-V relation for the process. (c) Obtain expressions for the work done by the gas, the heat input and the change in internal energy of the gas. Solution (a) Consider a closed system consisting of the ideal gas of mass m. The specific heat capacities of an ideal gas are functions of temperature only. Apply the first law to an infinitesimal change of state when the volume, pressure, and temperature are V, P and T respectively.
Q = dU + W
(E4.10.1)
Since the process is adiabatic the heat transfer is zero. The process is quasi-static and therefore the boundary work is given by PdV . For the ideal gas the increase in internal energy is mc v dT . Substituting these expressions in Eq. (E4.10.1) we obtain
0 = mcv dT + PdV
The equation of state of the ideal gas gives
(E4.10.2) (E4.10.3)
PV = mRT
where R is the gas constant of the ideal gas. We now manipulate Eqs. (E4.10.1), (E4.10.2) and (E4.10.3) to obtain the differential form of the P-V relation for the process. Differentiating Eq. (E4.10.3)
PdV + VdP = mRdT

Substituting for dT from Eq. (E4.10.4) in Eq. (E4.10.2) we have
(E4.10.4) (E4.10.5)
0 = (cv / R )( PdV + VdP ) + PdV

For an ideal gas
R = c p cv
168
Substituting for R in Eq. (E4.10.5) and simplifying the resulting equation
(c
/ cv )PdV + VdP = 0
(E4.10.6) (E4.10.7)
dV / V + dP / P = 0
where = c p / cv . In general, for an ideal gas is a function of T because cv and c p are functions of temperature. If this functional dependence is known, then in principle, Eq. (E4.10.7) could be integrated to obtain the P-V relation for the quasi-static, adiabatic process. (b) Now consider a special model of the ideal gas for which c p and cv are constants. Then, = c p / cv is also a constant, which allows easy integration of Eq. (E4.10.7) to obtain
ln(V ) + ln( P) = ln(C )
(E4.10.8)
where ln(C) is the constant of integration. Equation (E4.10.8) can be rearranged to the form
PV = C
(E4.10.9)
which is the required P-V relation for a quasi-static adiabatic process of an ideal gas. (c) In example 3.10 we obtained an expression for the work done in a quasi-static, polytropic process, [ PV n = C ] as
W = (P1V1 P2V2 ) /(n 1)
(E4.10.10)
Comparing Eq. (E4.10.9) with the polytropic law we find that for a quasi-static adiabatic process, n = . Hence using Eq. (E4.10.10) we obtain the work done in a quasi-static adiabatic process as:
W = (P1V1 P2V2 ) /( 1)
Now for the adiabatic process the heat interaction is zero. Applying the first law the increase in internal energy is
(E4.10.11)
U 2 U 1 = W = (P1V1 P2V2 ) /( 1) U 2 U 1 = mR(T1 T2 ) /( 1)

U 2 U 1 = m(c p cv )(T1 T2 ) /(c p / cv 1)
(E4.10.12)
Substituting from the ideal gas equation in Eq. (E4.10.12) we have
169
U 2 U 1 = mcv (T2 T1 )
Notice that we could have written the above equation directly for the increase in internal energy of an ideal gas. Example 4.11 0.2 kg of air initially at 0.6 bar and 20oC undergoes the cycle consisting of the three quasi-static processes shown in Fig. E4.11. The air is compressed isothermally to a pressure of 1.0 bar during the process 1-2. From 2 to 3 the air is heated in a constant volume process until the pressure is 2 bar. The adiabatic expansion from 3 to 1 returns the air to the initial state, completing the cycle. Calculate (i) the work done, the change in internal energy and the heat transfer during the processes 1-2, 2-3 and 3-1 and (ii) the net work done during the cycle. Assume that air is an ideal gas with constant specific heat capacities, cv = 0.718 kJkg-1K-1 and c p = 1.005 kJkg-1K-1 Solution We assume that air is an ideal gas with constant specific capacities. For air, and
R = c p cv = 1.005 0.718 = 0.287 kJkg-1K-1
= c p / cv = 1.005 / 0.718 = 1.4
Consider the isothermal compression from state 1 to 2, shown in Fig. E4.11. The work done by an ideal gas during an isothermal process was obtained in worked example 3.11 as
W = mRT ln(P1 / P2 )
Substituting numerical values in the above equation we have
W12 = 0.2 0.287 293 ln(0.6 / 1.0) = 8.59 kJ

Now for the isothermal process 1-2, T2 = T1 . Hence the change in internal energy of the ideal gas is
U 2 U 1 = mcv (T2 T1 ) = 0
Applying the first law to the process 1-2 we have
Q12 = U 2 U 1 + W12 = 0 8.591 = 8.591 kJ
170
Apply the ideal gas equation to the states 2 and 3
mR = P2V2 / T2 = P3V3 / T3
Since V2 = V3 for the constant volume process 2-3,
P2 / T2 = P3 / T3
1 / 298 = 2 / T3
Hence
P
T3 = 596 K
3
1 V
Fig. E4.11 A cyclic process
The work done in the constant volume process, 2-3, W23 = 0 . The change in internal energy is
U 3 U 2 = mcv (T3 T2 ) U 3 U 2 = 0.2 0.718 (596 298) = 42.79 kJ

Applying the first law to process 2-3
Q23 = U 3 U 2 + W23 = 42.79 + 0 = 42.79 kJ

Consider the quasi-static, adiabatic process 3-1. The work done is obtained by using the following expression derived in worked example 4.10
W31 = (P3V3 P1V1 ) /( 1) = mR (T3 T1 ) /( 1) W31 = 0.2 0.287 (596 298) /(1.4 1) = 42.76 kJ
171
The change in internal energy is
U 1 U 3 = mcv (T1 T3 ) U 1 U 3 = 0.2 0.718 (298 596) = 42.79 kJ

The heat transfer Q31 = 0 The net work done in the cycle is given by
Wnet = W12 + W23 + W31 = 8.59 + 0 + 42.76 = 34.2 kJ.

Example 4.12 A fixed quantity of steam of mass 0.4 kg at 200oC and 0.5 bar undergoes a cyclic process consisting of three quasi-static processes. The steam is compressed isothermally in a quasi-static process until the pressure is 4 bar. The steam then undergoes a constant volume process to 0.5 bar. This is followed by a constant pressure expansion to the initial state of 200oC. Calculate (i) the work done, the change in internal energy and heat transfer for each process, (ii) the net work done in the cycle and (iii) the net heat input. Solution Shown in Fig. E4.12 is the cycle executed by the steam. Consider the isothermal compression from 1-2. Since steam is not an ideal gas we must not use the expressions derived in worked example 3.11 for ideal gases. We will, therefore, extract the P-V data from the steam tables in [4] and estimate the work done numerically or graphically. The values of specific volume of superheated steam at different pressures for a constant temperature of 200oC are tabulated below. The work done during the quasi-static process 1-2 may be obtained using the expression
V2
W12 =
PdV
V1
The integration is carried out numerically using the trapezoidal-rule by dividing area under the P-V curve to a number of trapeziums. The work represented by the area of a typical trapezium is
Wi = ( Pi + Pi +1 )(Vi +1 Vi ) / 2
(i = 1,6)
172
P (Bar)
4 0.5 3
2 1 v (m3/kg)
Fig. E4.12 Cyclic process for steam
Table E4.12 Data for isothermal process i Pi10-5 (Pa) Vi (m3kg-1) Wi 10-5 (Jkg-1) 1 4.0 0.5345 0.637 2 3.0 0.7166 0.911 3 2.0 1.081 0.637 4 1.5 1.445 0.91 5 1.0 2.173 0.637 6 0.75 2.901 0.9093 7 0.5 4.356 -
The resulting numerical values are given in Table E4.12. The total work done per kg of steam is
W
i =1
i =6
= 464.4 kJkg-1
The total work done is
W12 = 0.4 464.2 = 185.68 kJ

The work done is negative because in the compression process work is done on the steam. The internal energies of the superheated steam at states 1 and 2 are obtained from the data tables in [4] as:
u1 = 2660 kJkg-1
and
u 2 = 2648 kJkg-1
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The increase in internal energy for the process 1-2 is
U 2 U1 = ms (u2 u1 ) = 0.4 (2648 2660) = 4.8 kJ

Applying the first law to process 1-2
Q12 = U 2 U 1 + W12 = 4.8 185.68 = 190.48 kJ

Consider the constant volume process 2-3. The quality at state 3 is found by equating the specific volumes at 2 and 3. Hence
0.5345 = x 3 3.239 + (1 x3 ) 0.1029 102 x3 = 0.1648

The internal energy at 3 is given by
u 3 = x3u g 3 + (1 x3 )u f 3 u 3 = 0.1648 2483 + (1 0.1648) 340 = 693.06 kJkg-1

The change in internal energy for process 2-3 is
U 3 U 2 = m s (u 3 u 2 ) U 3 U 2 = 0.4 (693.06 2648) = 781.98 kJ.

For the constant volume process 2-3, the work done, W23 = 0 Applying the first law to process 2-3
Q23 = U 3 U 2 + W23 = 781.98 kJ

Consider the constant pressure process 3-1. The increase in internal energy is
U 1 U 3 = m s (u1 u 3 ) U 1 U 3 = 0.4 (2660 693.06) = 786.78 kJ

The work done during the constant pressure process 3-1 is
W31 = m s P1 (v1 v3 ) W31 = 0.4 0.5 10 5 (4.356 0.5345) = 76.43 kJ

Applying the first law to the process 3-1 we have
Q31 = U 1 U 3 + W31 = 786.78 + 76.43 = 863.21 kJ
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The net work output for the cycle is
Wnet = W12 + W23 + W31 Wnet = 185.68 + 0 + 76.43 = 109.25 kJ

The net heat input for the cycle is
Qnet = Q12 + Q23 + Q31 Qnet = 190.48 781.98 + 863.21 = 109.25 kJ

As expected from the first law, for the cyclic process the net work output is equal to the net heat input. Example 4.13 An ideal gas of mass 0.8 kg is trapped in a well-insulated cylinder behind a frictionless insulated piston as shown in Fig. E4.13. The piston-cylinder set-up has a mass of 2.0 kg and a specific heat capacity of 0.8 kJkg-1K-1. The gas is compressed in a quasi-static manner from an initial state of 16 bar and 80oC to a final state where the volume is 40 percent of the initial volume. There is thermal equilibrium between the gas and the piston-cylinder set-up during the process due of the high thermal conductivity of the latter. The constant specific heat capacities of the gas are, cv = 0.72 kJkg-1K-1 and c p = 1.0 kJkg-1K-1. (a) Obtain an expression for the P-V relation for the process. (b) Calculate (i) the final temperature of the system, (ii) the work done on the gas and the change in internal energy, (iii) the change in internal energy of the piston-cylinder set-up and (iv) the heat interaction between the gas and the piston-cylinder set-up. Solution Let m be the mass and c the specific heat capacity at constant volume. The sub-scripts c and g denote quantities related to the pistoncylinder set up and the gas respectively. Consider a quasi-static process involving an infinitesimal change of state of the system consisting of the gas and the piston-cylinder set-up. The work done by the gas is given by
W = PdV
(E4.13.1)
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Gas P,V
Fig. E4.13 Piston-cylinder set-up
Since the piston-cylinder set-up and the gas are in thermal equilibrium their temperatures are equal. The total change in internal energy is
dU = m g c g dT + mc cc dT
Since the system is well-insulated,
(E4.13.2)
Q = 0
Applying the first law to the closed system we have
(E4.13.3) (E4.13.4) (E4.13.5)
Q = dU + W
(m g c g + mc cc )dT + PdV = 0
Applying the ideal gas equation
Substituting in Eq. (E4.13.4) from Eqs. (E4.13.1) to (E4.13.3) we obtain
PV = m g R g T
Differentiating Eq. (E4.13.6) we obtain
(E4.13.6)
PdV + VdP = m g R g dT
Substituting for dT in Eq. (E4.13.5) from Eq. (E4.13.7)
(E4.13.7)
(m g c g + mc cc )(VdP + PdV ) + m g R g PdV = 0 (m g c g + mc cc + m g R g ) PdV + (m g c g + mc cc )VdP = 0
m g c g + m g R g + mc c c m g c g + mc c c
dV dP + =0 V P
(E4.13.8)
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Upon integration Eq. (E4.13.8) gives the P-V relation as
PV = C
where the exponent is given by
(E4.13.9)
m g c g + m g R g + mc c c + m c m c g g c c
and C is the constant of integration. (b) For the ideal gas
R g = c p c v = 1.0 0.72 = 0.28 kJkg-1K-1

Substituting numerical values in the expression above for we obtain
0.8 0.72 + 0.8 0.28 + 2.0 0.8 = 1.1029 0.8 0.72 + 2.0 0.8
Applying Eq. (E4.13.9) to states 1 and 2 we have
16 V 1
Hence
1.1029
= P2 (0.4V1 )1.1029
P2 = 43.95 bar.
mR g = 16 V1 /(273 + 80) = 43.95 (0.4V1 ) / T2
Applying ideal gas equation to states 1 and 2 of the gas
(i) Hence
T2 = 387.86 K
(ii) The work done by an ideal gas, during a polytropic process, PV n = C was derived in worked example 3.10. Comparing the above process-law with Eq. (E4.13.9), n = . Hence
W12 = mg Rg (T1 T2 ) /( 1)
W12 = 0.8 0.28 (353 387.87) /(1.1029 1) = 75.91 kJ

The increase in internal energy of the ideal gas is
U g 2 U g1 = m g c g (T2 T1 ) U g 2 U g1 = 0.8 0.72 (387.87 353) = 20.085 kJ
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(iii) The increase in internal energy of the piston-cylinder set up is
U c 2 U c1 = mc cc (T2 T1 ) U c 2 U c1 = 2.0 0.8 (387.87 353) = 55.8 kJ

(iv) Applying the first law to the piston-cylinder set up
Q g c = U c 2 U c1 + Wc
The boundary work done by the piston-cylinder set-up is zero because its volume is constant. Hence
Q g c = U c 2 U c1 = 55.8 kJ
Applying the first law to the gas we have
Qc g = U g 2 U g1 + W12 Qc g = 20.085 75.91 = 55.8 kJ

Example 4.14 A cylinder of total volume 1.2 m3 is divided into two compartments A and B of equal volume by a thin, frictionless, adiabatic piston as shown in Fig. E4.14. Initially, compartment A contains air and B helium, both at 30oC and 100 kPa. The cylinder is well-insulated except for one face of A which is a diathermal wall. Heat is supplied to A in a quasi-static manner until a final equilibrium state where the pressure is 220 kPa is attained. Calculate (i) the final temperature of the helium and the air, (ii) the work done by the air and (iii) the heat input to the air. Assume that helium and air are ideal gases with the following specific heat capacities. For helium cv = 3.12 kJkg-1K-1, c p = 5.21 kJkg-1K-1 and for air cv = 0.72 kJkg-1K-1 and c p = 1.00 kJkg-1K-1. Solution Let sub-scripts i and f denote the initial and final states of the system. From the given data we have V Ai = V Bi = 0.6 m3, and T Ai = TBi = 303 K. The force balance on the frictionless piston in the initial and final equilibrium states gives:
PAi = PBi = 100 kPa
and
PAf = PBf = 220 kPa.
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The helium gas in B, which is treated as an ideal gas with constant specific heat capacities, undergoes a quasi-static adiabatic process. In worked example 4.10, we derived the P-V relation for such a process as
PV = C
For helium,
(E4.14.1)
= c p / cv = 5.21 / 3.12 = 1.67

100 (0.6)1.67 = 220 (VBf )1.67
Applying Eq. (E4.14.1) to the initial and final states we have
Hence Now
V Bf = 0.374 m3 V Af = 1.2 0.374 = 0.826 m3
Applying the ideal gas equation to the initial and final equilibrium states of the gases we obtain
mR = PiVi / Ti = Pf V f / T f
Substituting the pertinent numerical data for helium and air in the above equation
TBf = 220 0.374 303 / (100 0.6) = 415.51 K TAf = 220 0.826 303 / (100 0.6) = 917.69 K
Work done by the helium gas in B during the quasi-static adiabatic process is
WB = (PBiV Bi PBf V Bf ) /( 1)
WB = (100 0.6 220 0.374 ) /(1.67 1) = 33.25 kJ
Fig. E4.14 Piston-cylinder arrangement
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The work done by the air in A is used to compress the helium gas in B. Therefore
W A = WB = 33.25 kJ
Applying the ideal gas equation, the mass of air is
m A = 100 0.6 /(0.28 303) = 0.7072 kg

The increase in internal energy of the air is
U Af U Ai = m A cvA (T Af T Ai )
Substituting numerical values
U Af U Ai = 0.7072 0.72 (917.69 303) = 313 kJ.

Applying the first law to the air in A we have
Q A = U Af U Ai + W A = 313 + 33.25 = 346.25 kJ.

Example 4.15 A vertical cylinder of cross-sectional area 0.1 m2 is connected to a rigid pressure vessel of volume 0.4 m3 through a valve as shown in Fig. E4.15. Initially, the vessel contains air at 30oC and 6 bar and the cylinder is filled with air at 18oC and 1 bar. The piston is at a height of 0.15 m. The valve is now opened and air flows from the pressure vessel to the cylinder. The load on the piston is such that when the air pressure in the cylinder reaches 3.5 bar, the load just begins to move up. The load is moved a distance of 1 m while the air pressure in the cylinder remains constant at 3.5 bar. The load then hits a rigid stop but air from the vessel continues to flow into the cylinder until the pressure in the system is uniform and the temperature of the air is 18oC. Calculate (i) the final pressure in the system and (ii) the heat transfer between the system and the surroundings. Assume that air is an ideal gas with cv = 0.718kJkg-1K-1 and R = 0.287kJkg-1K-1. Neglect the volume of the piping and the valve. Solution We use the sub-scripts v and c to denote quantities related to the pressure vessel and the cylinder respectively. Let i represent the initial state and f the final state.
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Applying the ideal gas equation to the initial states of the pressure vessel and the cylinder we obtain
mci = 0.1 0.15 100 / (0.287 291) = 0.01796 kg mvi = 0.4 600 /(0.287 303) = 2.76 kg
The total mass of air is m = (0.01796 + 2.76) = 2.778 kg
Pamb
stop A V B
Mg
Fig. E4.15 Tank connected to piston-cylinder set-up
The final volume of air is
V f = 0.4 + (1.0 + 0.15) 0.1 = 0.515 m3

Applying the ideal gas equation to the final equilibrium state we have
Pf V f = mRT f Pf = 2.778 0.287 291 / 0.515 = 450.5 kPa

The work done by the air in the system is used to lift the piston with the load, Mg and to push the ambient air. Therefore
W = Mg ( z f z i ) + Pamb (V f Vi )
where z is the distance moved by the piston. If the area of the piston is A, then
W = ( Mg / A + Pamb )(V f Vi )
But
( Mg / A + Pamb ) = P = 3.5 bar,
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the pressure required to just lift the piston. Hence
W = P (V f Vi ) = 3.5 100 (0.515 0.4 0.015) = 35 kJ

Assume that the reference state for internal energy is 0oC. Then the final and initial internal energies are
U f = 2.778 0.718 18 = 35.9 kJ
U i = (2.76 0.718 30) + (0.01796 0.718 18) = 59.68 kJ

The increase in internal energy is
U f U i = 35.9 59.68 = 23.78 kJ

Applying the first law to the air we have
Qin = U f U i + Wout = 23.78 + 35 = 11.22 kJ

which is the heat transfer from the surroundings to the air. Example 4.16 A cylinder of diameter 0.15 m contains air behind a piston held in position by a rigid stop as shown in Fig. E4.16. The initial volume, pressure and temperature of the air are 5 10 3 m3, 8 bar and 25oC respectively. The mass of the piston is 250 kg and the ambient pressure is 1 bar. The stop is removed and the piston moves up until it hits a second rigid stop when the volume of the air is 7.5 10 3 m3. The frictional force between the piston and the cylinder is not negligible. The cylinder and the piston are well-insulated and their heat capacities are negligible. Calculate the pressure and temperature in the final equilibrium state. Solution The area of the piston is
A = D 2 / 4 = (0.15) 2 / 4 = 0.01767 m2
Apply the ideal gas equation to obtain the mass of air as
m = 8 10 2 5 10 3 /(0.287 298) = 0.04677 kg

When the stop is removed, the air does work to lift the piston, to push the surrounding air and to overcome the frictional force. The piston may also gain kinetic energy. After the piston hits the second stop and comes
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to rest the kinetic energy is converted to thermal energy due to the deformation of the piston and the stop. As we do not have sufficient information to estimate the latter effect using a simple model, we assume that the kinetic energy gained is negligible. Therefore the work done by the air is
Wa = M p gz + Po (V f Vi ) + W fr
where M p is the mass of the piston, z is the distance moved, Po is the ambient pressure, A is the area of the cylinder and W fr is the frictional work. The change in volume of the air is
(V f Vi ) = Az = (7.5 5.0) 10 3 = 2.5 10 3 m3

Now the frictional work done is converted to heat at the interface between the piston and the cylinder, (see Fig. E4.16). This heat, in general, is transferred to the piston-cylinder set-up and the air. Since the piston and cylinder have negligible thermal capacity, the internal energy stored in them can be neglected. Therefore all the heat generated by friction, Q fr is transferred to the air in the cylinder. Hence
Qia = Q fr = W fr
s2
(E4.16.1)
Po
z
Wfr Mp g Qfr
s1
Fig. E4.16 Piston-cylinder set-up with friction
Applying the first law to the air we have
Q fr = (U 2 U 1 ) + M p gz + Po A(V f Vi ) + W fr (E4.16.2)
Substituting from Eq. (E4.16.1) in Eq. (E4.16.2)
0 = U 2 U 1 + M p gz + Po (V f Vi )
183
ma cv (T2 T1 ) + M p g (V f Vi ) / A + Po (V f Vi ) = 0
Substituting the numerical values we obtain
ma c v (T2 T1 ) + (250 9.8 10 3 / 0.01767 + 100) 2.5 10 3 = 0
0.04677 0.718 (T 2298) + 0.596 = 0

Hence
T2 = 280.28 K
Note that if the heat capacity of the cylinder is not negligible, then a fraction of the heat generated by friction at the interface will be absorbed by the cylinder as internal energy. The rest of the heat will flow into the gas. The analysis of such a scenario is beyond the scope of this book.
Example 4.17 A spring-loaded-piston-cylinder arrangement shown in Fig. E4.17 contains 3.5 10 4 m3 of air at 30oC. The mass of the piston is 10 kg and the ambient pressure is 100 kPa. Initially, the linear spring exerts a force of 500 N on the piston and, it is compressed by 0.015 m. The diameter of the piston is 0.09 m. Heat is supplied to the air in a quasi-static matter until the pressure of the air is 300 kPa. Calculate (i) the spring constant, (ii) the work done on the spring, (iii) the work done on the surrounding air, (iv) potential energy gained by the piston, (v) the work done by the air, (vi) the final temperature of the air, (vii) the change in internal energy of the air and, (viii) the heat transfer to the air. Assume that air is an ideal gas with cv = 0.718 kJkg-1K-1 and R = 0.287 kJkg-1K-1. Solution (i) The spring constant is,
k = 500 / 0.015 = 33.33 kNm-1

Area of the piston is
A = 0.09 2 / 4 = 6.36 10 3 m2 Let the compression of the spring in the final state be x1 m
Force balance on the piston for the final equilibrium state gives
Pf A = Mg + Po A + kx1
184
300 6.36 10 3 = 10 9.81 10 3

+ 100 6.36 10 3 + 33.33 x1
Hence
x1
x1 = 0.0352 m
(ii) Work done on the spring is
Ws =
kxdx = k ( x1 x0 ) / 2
x0
Ws = 33.33 10 3 (0.0352 2 0.015 2 ) / 2 = 16.9 J
Po
Mg
Heat
Fig. E4.17 Spring-loaded piston cylinder set-up
(iii) Work done on the surrounding air,
Wo = P0 A( x1 x0 ) Wo = 100 10 3 6.36 10 3 (0.0352 0.015) = 12.85 J

(iv) Potential energy gained by the piston,
W p = Mg ( x1 x0 ) = 10 9.81 (0.0352 0.015) = 1.98 J

(v) Work done by the air is given by
Wa = Ws + Wo + W p = 16.92 + 12.85 + 1.98 = 31.75 J
185
(vi) The initial pressure is,
Pi = Po + Mg / A + kxo / A
Pi = 100 + (10 9.81 10 3 + 33.33 0.015) /(6.36 103 )
Hence
Pi = 194.04 kPa
Applying the ideal gas we obtain the mass of air as
m = P1V1 / RT1
m = 194.04 3.5 10 4 /(0.287 303) = 0.781 10 3 kg
The final volume of air is
V f = Vi + A( x1 x0 )
V f = 3.5 10 4 + 6.36 10 3 (0.0352 0.015) = 0.478 10 3 m3

Applying the ideal gas equation to the final state
T f = Pf V f / mR
T f = 300 0.478 10 3 /(0.781 10 3 0.287) = 639.76 K

(vii) The change in internal energy of the air is
U f U i = mcv (T f Ti )
U f U i = 0.781 10 3 0.718 (639.76 303) = 188.84 J

(viii) Applying the first law to the air we obtain the heat input as
Qa = U f Ui + Wa = 188.84 + 31.75 = 220.6 J

Example 4.18 A well-insulated piston-cylinder device has 0.5 kg of air at 30oC and 3 bar. Installed inside the cylinder is a small heating element of negligible thermal capacity as shown in Fig. E4.18. A steady current of 6 A is passed through the heating element for 30s. The air expands slowly at constant pressure until the volume increases by 40 percent. Assume that air is an ideal gas, and cv = 0.718 kJkg-1K-1 and R = 0.287 kJkg-1K-1. Calculate (i) the work done by the air, (ii) the change in internal energy of the air, and (iii) the resistance of the heating element.
186
Solution From the ideal gas equation we obtain the initial volume of the air as
Vi = 0.5 0.287 303 /(3 100) = 0.1449 m3

The final volume is
V f = 1.4Vi = 1.4 0.1449 = 0.2029 m3

Work done by the air in the constant pressure process is
Wa = P (V f Vi ) = 300 (0.2029 0.1449) = 17.4 kJ

Applying the ideal gas equation to the initial and final states
mR = PV f / T f = PVi / Ti
P
Ve
Fig. E4.18 Piston-cylinder set-up with electrical heater
Hence
T f = 1.4Ti = 1.4 303 = 424.2 K U f U i = mcv (T f Ti ) U f U i = 0.5 0.718 (424.2 303) = 43.51 kJ
Change in internal energy of the air is
We apply the first law to the closed system consisting of the air and the heater. In chapter 3, we showed that electrical energy supplied to the heating element is a work interaction. Since the cylinder is
187
well-insulated, the heat interaction between the system and the surroundings is zero. Applying the first law we have
0 = U f U i + Wa + Wel
Wel = 43.51 17.4 = 60.91 kJ

The total electrical work supplied to the system is
Wel = Ve I = I 2 R
where Ve is the voltage across the heater, R is the resistance of the heater, I is the current and is time. Substituting the numerical values in the above equation
R = 60.91 10 3 /(6 2 30) = 56.4

The resistance of the heater is 56.4 ohms. Example 4.19 The specific heat capacity of an ideal gas varies linearly with temperature according to the relationship, cv = c0 + c1T in the temperature range T1 to T2 , where c0 and c1 are constants. Obtain expressions for change in internal energy, the work done and the heat transfer when the gas undergoes the following quasi-static processes from T1 to T2 (i) constant volume heating, (ii) constant pressure expansion and (iii) adiabatic process. Solution (i) Consider a quasi-static constant volume process. The work done is zero. The change in internal energy is given by
U 2 U 1 = dU = m cv dT = m (co + c1T )dT

T1 T1 T1
T2
T2
T2
Integrating the above equation we have
U 2 U 1 = mco (T2 T1 ) + mc1 (T2 T1 ) / 2

U 2 U 1 = m[c0 + c1 (T1 + T2 ) / 2](T2 T1 ) = mcm (T2 T1 )
188
where
c m = c0 + c1 (T1 + T2 ) / 2 ,
is the specific heat capacity evaluated at the arithmetic mean temperature Tm = (T1 + T2 ) / 2 of the process, The heat transfer is obtained by applying the first law as
Qin = U 2 U 1 = mc m (T2 T1 )
(ii) Consider a constant pressure process. The change in internal energy is the same as in (i) above because the internal energy is a property and therefore independent of the process. For an ideal gas, the change on internal energy depends only on the initial and final temperatures. For a constant pressure process, the work done by the ideal gas is
W = P(V2 V1 ) = mR(T2 T1 )
Applying the first law, the heat input is
Qin = U 2 U 1 + W = mc m (T2 T1 ) + mR(T2 T1 ) Qin = m(c m + R)(T2 T1 )

(iii) For an adiabatic process the heat transfer is zero. The change in internal energy is the same as in (i) above because it is a property and is therefore pathindependent. Applying the first law
Qin = (U 2 U 1 ) + Wout Wout = (U 2 U 1 ) = mc m (T1 T2 )

. Example 4.20 In a heat transfer experiment a copper sphere of diameter 0.06 m is cooled in a stream of air at a constant temperature of 20oC as shown in Fig. E4.20. The initial temperature of the sphere is 60oC. The rate of heat flow (kW) from the outer surface of the sphere to the air is given by
Q / dt = 0.5 A(T 20) ,

where A(m2) is the surface area of the sphere and T(oC) is the temperature of the sphere which may be assumed uniform because of the high thermal conductivity of copper. The density and specific heat capacity of copper are 8900 kgm-3 and 0.4 kJkg-1K-1 respectively.
189
(a) Obtain in differential-form an equation for the time variation of the temperature of the sphere. (b) Calculate the temperature of the sphere 90 s after it is placed in the air stream. (c) What is the final steady temperature of the sphere? Solution Consider the copper sphere as a closed system. We apply the rate-from of the first law to the system
Q / dt = dU / dt + W / dt
(E4.20.1)
The boundary work done is zero because the volume of the sphere is constant. The heat transfer rate is given as
Q / dt = 0.5 A(T 20)

The internal energy of the system is given by
(E4.20.2) (E4.20.3)
U = mcT
Air flow V
Fig. E4.20 Cooling of a copper sphere
where m is the mass and c the specific heat capacity of copper. The reference state for the internal energy is at 0oC. Note that for a solid like copper, the c v and c p are assumed equal because of the low compressibility. Substituting in Eq. (E4.20.1) from Eqs. (E4.20.2) and (E4.20.3) we have
0.5 A(T 20) = d (mcT ) / dt

The area and mass of a sphere are give by
(E4.20.4)
A = 4r 2
and
m = 4r 3 / 3
(E4.20.5)
where r is the radius of the sphere and is the density of copper.
190
Substituting from Eq. (E4.20.5) in Eq. (E4.20.4) we obtain
dT / dt = 0.5 3 (T 20) /(rc )

Substituting the given numerical values in the above equation
dT / dt = 0.01404 (T 20)
(E4.20.6)
Equation (E4.20.6) is a first-order differential equation which can be written as
dT /(T 20) = 0.01404dt
(E4.20.7)
Integrating both sides of Eq. (E4.20.7) and substituting the initial temperature at time t = 0 as 60oC we have
(T 20) / 40 = exp(0.01404t )
Hence the temperature after 90 s is given by the equation
(E4.20.8)
(T1 20) / 40 = exp(0.01404 90) = 0.2826

Thus T1 = 31.3 oC From Eq. (E4.20.8), the steady-state temperature as t is 20oC. Problems P4.1 A well-insulated tank, of negligible thermal capacity contains 15 kg of liquid at 25oC. A paddle-wheel of mass 1.5 kg is placed within the liquid and rotated by a motor which receives a steady energy input of 0.5 kW from a battery. The specific heat capacities of the liquid and the wheel are 1.2 kJkg-1K-1 and 0.85 kJkg-1K-1 respectively. The motor is switched on for 300s and then switched off. (a) Calculate the final temperature of the liquid and wheel assuming that it is uniform. (b) Treating (i) the liquid and wheel, (ii) the battery and (iii) the composite system as closed systems, calculate the work transfer, the heat transfer and the change in internal energy. State all assumptions clearly. [Answers: (a) 32.8oC, (b) (i) Win = U liq = 150 kJ, (ii) U bat = Wout = 150 kJ, (iii) U system = 0 kJ] P4.2 A strip of metal of mass 0.05 kg and specific heat capacity 0.48 kJkg-1K-1 is pressed against the surface of a grinding wheel of radius
191
0.35 m with a radial force of 0.045 kN. The coefficient of friction between the surfaces of the wheel and the metal is 0.55. The wheel is rotating at a steady speed of 8 rs-1. (a) Calculate temperature rise in the metal strip in 20 s. Assume that there is no heat loss to the surroundings and that the grinding wheel has a low thermal conductivity. (b) Treating the metal strip as a closed system calculate the heat interaction, the work interaction and the change in internal energy. State all assumptions clearly. [Answers: (a) 57.75oC, (b) At the sliding surface , for the strip, Q =U =Q ] W P4.3 A quantity of wet steam of mass 0.15 kg is trapped in a cylinder behind the leak-proof piston. The initial pressure and quality of the steam are 3 bar and 0.7 respectively. Heat is supplied to the steam at constant pressure until the volume becomes 0.1 m3. (i) Calculate the work done, the change in internal energy and the heat transfer. (ii) If the piston is held fixed and the cylinder is cooled in a quasi-static manner until condensation of steam just begins, calculate the work done, change in internal energy and the heat transfer during the process. [Answers: (i) 10.9 kJ, 98.1 kJ, 109 kJ, (ii) 0 kJ, -9.47 kJ, -9.47 kJ] P4.4 A fixed quantity of air of mass 0.4 kg undergoes a cycle consisting of three processes. The pressure and temperature of state 1 are 1.0 bar and 30oC respectively. During the process 1-2 the air is compressed isothermally to a pressure of 8 bar. The air then expands at constant pressure to state 3. The final process 3-1 is a polytropic process, with the condition, PV 1.3 = constant. Assume that air is an ideal gas with cv = 0.718 kJkg-1K-1 and c p = 1.005 kJkg-1K-1. Calculate (i) the work done, the change in internal energy and the heat transfer during the three processes, 1-2, 2-3 and 3-1, (ii) the ratio of the net work done to the total heat supplied to the air and (iii) the efficiency of the cycle. [Answers: (i) W12 = 72.33 kJ, U 12 = 0 , Q12 = 72.33 kJ, W23 = 21.42 kJ, U 23 = 53.58 kJ, Q23 = 75.0 kJ, U 31 = 53.58 kJ, W31 = 71.39 kJ, Q31 = 17.8 kJ, (ii) Wnet = 20.48 kJ, Qin = 92.8 kJ, (iii) = Wnet / Qin = 22% ]
192
P4.5 A fixed quantity of wet steam of mass 0.4 kg undergoes a polytropic expansion according to the relation, PV 1.2 = constant, from an initial pressure of 4.5 bar and quality 0.8 to a final pressure of 2.5 bar. Calculate the work done, the change in internal energy and the heat transfer during the polytropic process. [Answers: W12 = 27.87 kJ, U 12 = 52.2 kJ, Q12 = 24.33 kJ] P4.6 A rigid tank of volume 0.25 m3 contains argon at a pressure of 4 bar and temperature 30oC. The tank is connected to a piston-cylinder apparatus, through a valve, which is initially closed and the piston rests at the bottom of the cylinder. The mass of the piston and the ambient pressure are such that a pressure of 2 bar has to act on the inside of the piston to just lift it. The valve is now opened and remains open until the system attains the final equilibrium state with a uniform temperature of 30oC. Calculate (i) the work done by the argon during the process, (ii) the change in internal energy of the argon and (iii) the heat transfer to the system. Assume that argon is an ideal gas with cv = 0.312 kJkg-1K-1 and c p = 0.52 kJkg-1K-1. [Answers: (i) W12 = 50 kJ, (ii) U 12 = 0 , (iii) Q12 = 50 kJ] P4.7 A well-insulated rigid tank is divided into two compartments 1 and 2 by a non-conducting membrane. Initially, the compartment 1 contains nitrogen at 100 kPa and 300 K while compartment 2 has nitrogen at 300 kPa and 400 K. The volume of compartment 1 is three times the volume of compartment 2. The membrane is now ruptured and the gases in the two compartments mix to attain a final equilibrium state. Calculate the final pressure and temperature of the nitrogen. [Answers: 150 kPa, 342.9 K] P4.8 A thin electrical heating element of resistance 100 ohms and thermal capacity 0.05 kJK-1 is located inside a piston-cylinder set-up. The well-insulated cylinder contains 0.2 kg of air with a uniform initial temperature of 20oC. A current of 2 A is passed through the heater for 20 s and then switched off. The air undergoes a constant pressure process and the system attains a final equilibrium state. Calculate (i) the
193
final equilibrium temperature and (ii) the work done by the air. [Answers: (i) 51.87oC, 1.83 kJ] P4.9 The cylinder, shown in Fig. P4.9, is divided into two chambers A and B by the thin spring-loaded piston which is free to move inside the cylinder in a frictionless manner. The chamber A contains 0.5 10 3 kg of helium gas while the chamber B, where the spring is located, is evacuated. The length of the cylinder is 1.8 m and its cross sectional area is 0.005 m2. The linear spring has a spring constant of 2 kNm-1. The initial pressure and temperature of the helium are 100 kPa and 30oC respectively. The gas is heated slowly until the temperature is 200oC. Calculate (i) the change in internal energy of the gas, (ii) the work done by the gas and (iii) the heat transfer during the process. Assume that helium is an ideal gas with cv = 3.116 kJkg-1K-1 and c p = 5.193 kJkg-1K-1. [Answers: (i) 0.265 kJ, (ii) 0.0537 kJ, (iii) 0.3185 kJ]
Fig. P4.9 Spring-loaded piston-cylinder set-up
P4.10 A stream of air at a constant temperature of 15oC passes over a 0.75 kW electrical heater. Before the current is switched on the heater temperature is 15oC. The rate of heat flow (kW) from the outer surface of the heater to the air can be expressed as
Q / dt = 0.01 (T 15) ,
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where T (oC) is the temperature of the heater which may be assumed uniform. The heat capacity of the heater is 0.5 kJK-1. Calculate (i) the temperature of the heater 30 s after it is switched on and (ii) the final steady temperature of the heater. [Answers: (i) 48.8oC, (ii) 90oC] References
1. Cravalho, E.G. and J.L. Smith, Jr., Engineering Thermodynamics, Pitman, Boston, MA, 1981. 2. Jones, J.B. and G.A. Hawkins, Engineering Thermodynamics, John Wiley & Sons, Inc., New York, 1986. 3. Reynolds, William C. and Henry C. Perkins, Engineering Thermodynamics, 2nd edition, McGraw-Hill, Inc., New York, 1977. 4. Rogers, G.F.C. and Mayhew, Y.R., Thermodynamic and Transport Properties of Fluids, 5th edition, Blackwell, Oxford, U.K. 1998. 5. Tester, Jefferson W. and Michael Modell, Thermodynamics and Its Applications, 3rd edition, Prentice Hall PTR, New Jersey, 1996. 6. Van Wylen, Gordon J. and Richard E. Sonntag, Fundamentals of Classical Thermodynamics, 3rd edition, John Wiley & Sons, Inc., New York, 1985. 7. Zemansky, M., Heat and Thermodynamics, 5th edition, McGraw-Hill, Inc., New York, 1968.

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Chapter 4

The First Law of Thermodynamics

Fig. 4.1 Cyclic process

In the cyclic-integral notation Eq. (4.2) can be written in the form

The First Law of Thermodynamics

Q12 A + Q21B = W12 A + W21B

Q12 A + Q21C = W12 A + W21C

Q21B W21B = Q21C W21C

Q1 2 W12 = Increase in internal energy Q1 2 = ( E 2 E1 ) + W12

The First Law of Thermodynamics

Fig. 4.3 An uncoupled system

The First Law of Thermodynamics

mdu (T , P ) = Q P(T , V ) Adz

The First Law of Thermodynamics

The First Law of Thermodynamics

The First Law of Thermodynamics

(4.37) (4.38) (4.39) (4.40)

The First Law of Thermodynamics

Equation (4.41) can be expressed in terms of the specific heat capacities as

[U ] = J, [H ] = J, [CV ] = JK-1, [C P ] = JK-1,

In Sec. 2.7 we obtained the following equation for the temperature.

The First Law of Thermodynamics

Fig. 4.5 Variation of

predicted by the Kinetic Theory

The First Law of Thermodynamics

u = xu g + (1 x)u f h = xhg + (1 x)h f

Applying the first law to a change of state

Qa1b = U b U a + Wa1b = 82 = U b U a + 32 U b U a = 50 kJ Qa 2b = U b U a + Wa 2b = 50 +12 = 62 kJ Qb 3a = U a U b + Wb3a = 50 + 22 = 28 kJ Wa 2b = Wa 2 + W * 2b = 12 = Wa 2 + 0 , Wa 2 = 12 kJ

The First Law of Thermodynamics

Fig. E4.2 P-V diagram

Wa1b = W * a1 + W1b = 32 = W1b + 0 ,

Qa 2 = U 2 U a + Wa 2 = (42 2) + 12 = 52 kJ Qa 2b = Qa 2 + Q2b = 52 + Q2b = 62 , Q2b = 10 kJ

U 1 = ( m s c s ) 200 + (mw c w ) 25 + (mt ct ) 25

Fig. E4.3 Heat treatment operation

The final internal energy is

0.75 0.48 (200 50) + 1.2 0.48 (25 50)

The First Law of Thermodynamics

U s = ms c s (50 200) = 0.75 0.48 150 = 54 kJ Qw s = U s + Ws w = 54 kJ

Wt w = 0 U t = mt ct (50 25) = 1.2 0.48 25 = 14.4 kJ Qwt = Ut + Wt w = 14.4 kJ

U w = m w c w (50 25) = 0.377 4.2 25 = 39.59 kJ Qs w + Qt w = U w + Wwt + Ww s = 39.6 kJ

The First Law of Thermodynamics

W w v = 0 = m c (dT / dt ) + m c (dT / dt ) U w w w w wh wh wh = 4 4.2 0.012 + 0.8 0.012 = 211.2 W U w

Substituting in Eq. (E4.4.3)

6.912 = 211.2 + 0 + W w m W w m = 218.11 W

Q a s = U s + Ws a = U w + U v + U b + Ws a = 6.912 + 211.2 218.11 = 0 U s

Fig. E4.5 Projectile in block

Substituting numerical values in Eq. (E4.5.1)

Vsf = 3 10 3 250 /(5 + 3 10 3 ) = 0.15 ms-1

The First Law of Thermodynamics

Ei = m pV pi / 2 + m p c p T pi + mb cbTbi E f = (m p + mb )Vsf / 2 + m p c p T pf + mb cbTbf

E i = 0.003 (250) 2 / 2 + 0.003 0.48 10 3 20

E f = 5.003 (0.15) 2 / 2 + 0.003 0.48 10 3 T pf

Fig. E4.6 Flywheel with disc brake

= [I (d / dt ) + (mc) (dT / dt ) + (mc) (dT / dt )] = 0 E s a a b b

= 5 10 0.5 10 3 + 0.3 (dT / dt ) + 0.75 0.02 = 0 E s a

dTa / dt = 0.033 oCs-1.

The First Law of Thermodynamics

Q i a = U a = ( mc ) a (dTa / dt ) = 0.3 0.0330 = 0.0099 kW

Equation (E4.6.5) can be written as

Substituting numerical values in the above equation we have

m h cvhT fh + mc cvcT fc = m h cvhTih + mc cvc Tic

The First Law of Thermodynamics

The mass of hydrogen and carbon dioxide are